DE69817319T2 - Silanyl triazines as light stabilizers - Google Patents

Description

The present invention relates to new s-triazines, a process for their preparation and their use of which as UV-B filters in light protection compositions, in particular for the production of a cosmetic composition that is suitable for human skin protect from sunlight.

Many sunscreens were in described and developed in the past, being 1,3,5-triazines as UV-B stabilizers were proposed. An example of such a triazine compound is tris (2-ethylhexyl) trisbenzoic acid 4,4 ', 4' '- (1,3,5-triazine-2,4,6-triyltriimino), which is sold under the name UVINUL T-150.

In the German Offenlegungsschrift DE-OS 3 206 3987 equivalent to U.S. Patent 4,617,390, s-triazine derivatives are disclosed which strongly absorb and are obtained in the UV-B region by reacting trichlorotriazine with p-aminobenzoic acid esters. However, these compounds are very poorly soluble in solvents which are generally used in sunscreen formulations, which limits their use as an ingredient in emulsions and cosmetic formulations, especially when an increased dosage of the sunscreen is necessary. In addition, these filters tend to crystallize on the skin, leaving a sandy feeling on the skin and significantly reducing the sun protection factor (SPF).

It has now been found that connections general formula I below except that it is in the W-B range absorb, also good solubility in solvents show that usually can be used in sunscreens.

worin
W¹, W² und W³ jeweils unabhängig C₁-C₂₀-Alkyl oder eine Gruppe SpSil bedeuten;
X¹, X² und X³ jeweils unabhängig O oder NH bedeuten;
Sp eine Spacergruppe bedeutet;
Sil ein Silan, Oligosiloxan oder eine Polysiloxaneinheit bedeutet;
mit dem Vorbehalt, dass mindestens einer der Reste W¹, W² und W³ SpSil bedeutet, Gegenstand der vorliegenden Erfindung.Thus compounds of general formula I

wherein
W ¹ , W ² and W ³ each independently represent C ₁ -C ₂₀ alkyl or a group SpSil;
X ¹ , X ² and X ³ each independently represent O or NH;
Sp represents a spacer group;
Sil represents a silane, oligosiloxane or a polysiloxane unit;
with the proviso that at least one of the radicals W ¹ , W ² and W ^{3 is} SpSil, is the subject of the present invention.

W ¹ , W ² and W ^{3 are} preferably SpSil or W ¹ and W ^{2 are} C ₁ -C ₂₀ -alkyl, preferably 2-ethylhexyl and W ³ is SpSil.

X ¹ , X ² and X ^{3 are} preferably oxygen or X ¹ and X ^{2 are} oxygen and X ³ is NH.

The term "spacer group" in this context refers to a divalent C ₃ -C ₁₂ alkyl or alkylene chain which connects a silane, oligosiloxane or polysiloxane unit to the triazine residue. In the chains, one or more carbon atoms can be replaced by oxygen atoms, which leads to groups such as -C ₁ -C ₆ alkyl-OC ₁ -C ₅ alkyl-, e.g. B. - (CH ₂ ) ₂ -O (CH ₂ ) ₂ - or - (CH ₂ ) ₄ -O- (CH ₂ ) ₂ -; -C ₁ -C ₆ alkenyl-OC ₁ -C ₅ alkyl-, e.g. B. -C (= CH ₂ ) - (CH ₂ ) ₂ -O- (CH ₂ ) ₄ -; -C ₁ -C ₄ alkyl-OC ₁ -C ₄ alkyl-OC ₁ -C ₂ alkyl, e.g. B. - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -O- (CH ₂ ) ₂ - and the like.

The term "divalent C ₃ -C ₁₂ alkyl chain" includes straight-chain or branched saturated hydrocarbon radicals, such as 3-propylene, 2-propylene, 2-methyl-3-propylene, 3-butylene, 4-butylene, 4-pentylene, 5- Pentylene, 6-hexylene, 12-dodecylene and the like.

The term "divalent C ₃ -C ₁₂ alkylene chain" encompasses straight-chain or branched unsaturated hydrocarbon radicals which contain one or more double bonds, such as 2-propen-2-ylene, 2-propen-3-ylene, 2-methyl-3-propenylene , 3-buten-3-ylene, 4-buten-3-ylene, 4-penten-4-ylene, 5-penten-4-ylene, (3-methyl) penta-2,4-diene-4- or - 5-ylene, 11-dodecen-11-ylene and the like.

Preferred spacer groups are: - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH) (CH ₃ ) - (CH ₂ ) -, - (CH ₂ ) ₂ - CH = CH-, -C (= CH ₂ ) -CH ₂ -, -C (= CH ₂ ) - (CH ₂ ) ₂ -O- (CH ₂ ) ₄ -, (CH ₂ ) ₄ -O- (CH ₂ ) ₂ -.

The term "silane" in this context refers to a group SiR ¹ R ² R ³ , wherein R ¹ , R ² and R ³ each independently represent C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or phenyl.

The terms "alkyl" and "alkoxy" can be straight chain or be branched radicals with the specified number of carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, 2-ethylhexyl, thexyl, (1,1,2-trimethylpropyl) or methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, 2-ethyloxy, thexoxy.

Examples of the group SiR ¹ R ² R ³ are: Si (CH ₂ -CH ₃ ) ₃ , Si (CH ₂ -CH ₂ -CH ₃ ) ₃ , Si (isopropyl) ₃ , Si (tert-butyl) ₃ , SiMe ₂ tert. -Butyl, SiMe ₂ -thexyl, Si (OMe) ₃ , -Si (OEt) ₃ , SiPh ₃ and the like, preferably Si (CH ₂ -CH ₂ ) ₃ - and Si (CH ₂ -CH ₂ -CH ₂ ) _3rd

worin
A eine Bindung an den Spacer bedeutet;
R C₁-C₆-Alkyl oder Phenyl bedeutet;
r 1 bis 9, bevorzugt 1 bis 3, bedeutet.The term "oligosiloxane" in this context refers to groups of the general formula SiR ¹⁰ _m (OSiR ¹⁰ ₃ ) n with m = 0, 1 or 2; n = 3, 2 or 1 and m + n = 3, or a group according to one of the general formulas IIa, IIa 'or IIb

wherein
A represents a bond to the spacer;
RC ₁ -C ₆ alkyl or phenyl;
r is 1 to 9, preferably 1 to 3.

worin
A eine Bindung an den Spacer ist;
R¹¹ C₁-C₆-Alkyl oder Phenyl bedeutet;
s einen Wert von 4 bis 250, bevorzugt 5 bis 150 hat;
t einen Wert von 5 bis 250, bevorzugt 5 bis 150, bevorzugter einen statistischen Mittelwert von etwa 60 hat;
q einen Wert von 1 bis 30, bevorzugt 2 bis 10, bevorzugter einen statistischen Mittelwert von etwa 4 hat.The term "polysiloxane" in this context refers to groups of the general formula IIIa or IIIb

wherein
A is a bond to the spacer;
R ^{11 represents} C ₁ -C ₆ alkyl or phenyl;
s has a value of 4 to 250, preferably 5 to 150;
t has a value of 5 to 250, preferably 5 to 150, more preferably a statistical mean of about 60;
q has a value of 1 to 30, preferably 2 to 10, more preferably a statistical mean of about 4.

The radicals R ¹⁰ and R ¹¹ are preferably C ₁ -C ₆ alkyl, more preferably C ₁ -C ₄ alkyl, most preferably methyl.

worin
X O oder NH bedeutet;
Sp' eine geradkettige oder verzweigte gesättigte oder einfach oder mehrfach ungesättigte Kohlenwasserstoffgruppe mit 3 bis 12 Kohlenstoffatomen bedeutet;
Sil' die Gruppe SiR¹R²R³ bedeutet, worin R¹, R² und R³ jeweils unabhängig C₁-C₆-Alkyl, C₁-C₆-Alkoxy oder Phenyl bedeuten oder ein Oligosiloxan der Formel -SiMe_m(OSiMe₃)_n, worin Me Methyl ist und m 0, 1 oder 2 ist, n 1, 2 oder 3 ist und m + n 3 ist oder ein Oligosiloxan gemäß einer der Formeln A, A' und B

worin Me Methyl ist und u 0 bis 6 ist.In a particular embodiment of the invention, W ¹ , W ² and W ³ mean Sp'Sil '. This embodiment relates to compounds of the formula Ia:

wherein
X represents O or NH;
Sp 'represents a straight-chain or branched saturated or mono- or polyunsaturated hydrocarbon group having 3 to 12 carbon atoms;
Sil 'denotes the group SiR ¹ R ² R ³ , in which R ¹ , R ² and R ³ each independently represent C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or phenyl or an oligosiloxane of the formula -SiMe _m ( OSiMe ₃ ) _n , where Me is methyl and m is 0, 1 or 2, n is 1, 2 or 3 and m + n 3 or an oligosiloxane according to one of the formulas A, A 'and B

where Me is methyl and u is 0 to 6.

Particularly preferred compounds of the formula I are:
2,4,6-trianilino-p- {carbo-4 '- (1,1,3,3,3-pentamethyldisi-loxanyl) -1'-butyloxy} -1,3,5-triazine,
2,4,6-trianilino-p- {carbo-4 '- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) -1'-butyloxy} -1,3,5-triazine,
2,4,6-trianilino-p- {carbo-2'-methyl-3 '- (1,1,3,3,3-pentamethyldisiloxanyl) -1'-propyloxy} -1,3,5-triazine,
2,4,6-trianilino-p- {carbo-5 '- (1,1,3,3,3-pentamethyldisi-loxanyl) -1'-pentyloxy} -1,3,5-triazine,
2,4,6-trianilino-p- {carbo-3 '- (1,1,3,3,3-pentamethyldisi-loxanyl) -1'-propyloxy} -1,3,5-triazine,
2,4,6-trianilino-p- {carbo-4 '- (triethylsilyl) -1'-but-3-enyloxy} -1,3,5-triazine,
2,4,6-trianilino-p- {carbo-4 '- (triethylsilyl) -1'-butyloxy} -1,3,5-triazine and
2,4,6-trianilino-p- {carbo-7 '- (triethylsilyl) -4'-oxaheptyloxy} -1,3,5-triazine,
2,4,6-trianilino-p- {carbo-7 '- (1,1,3,3,3-pentamethyldisi-loxanyl) -4'-oxaheptyloxy} -1,3,5-triazine,
2,4-dianilino-p-carbo- (2'-ethylhexyloxy) -6-anilino-p- {carbo-7 '- (1,1,3,3,3-pentamethyldisiloxanyl) -4'-oxaheptyloxy} -1 , 3,5-triazine,
2,4-dianilino-p-carbo- (2'-ethylhexyloxy) -6-anilino-p- {carbo-7 '- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) -4' oxaheptyloxy} -1,3,5-triazine,
2,4-dianilino-p-carbo- (2'-ethylhexyloxy) -6-amino {N- (2 '(1,1,1,3,5,5,5-heptamethyltrisiloxanyl) allyl) -p-benzamidyl} -1,3,5-triazine or
a polysiloxane whose statistical mean corresponds to the following formula:

The compounds according to the present Invention absorb UV radiation in the range from 290 to 320 nm and show improved solubility in lipophilic solvents. Can continue they are easily dispersed in emulsions and have a relative little tendency to crystallize in emulsions or on the skin. So you can the compounds of the present invention for the preparation of Light protection compositions are used, in particular for Preparation of a cosmetic composition that is suitable to protect human skin from sunlight. This Products can applied in high concentrations, which is an improved Sun protection supplies. Effects such as accumulation or aggregation or crystallization, which means a loss of effectiveness, are lower in the emulsions and on the skin.

Another subject of the present Invention is a process for the preparation of the compounds of Formula I.

Another subject of the present Invention is a sunscreen composition containing one or more Contains compounds of formula I as a sunscreen.

worin Sil und X wie oben definiert sind; Sp'' die gleiche Bedeutung hat, wie für Sp oben definiert, außer dass es einen Grad an Ungesättigtheit hat, der um eins höher ist als bei Sp. In anderen Worten ist, wenn Sp'' eine Doppelbindung hat, Sp gesättigt und wenn Sp" eine Dreifachbindung oder zwei Doppelbindungen hat, hat Sp eine Doppelbindung. Stufe II

worin Sil, Sp und X wie oben definiert sind. Stufe III

worin Sil, Sp und X wie oben definiert sind.The synthesis of the compounds of the formula I in which W ¹ , W ² and W ^{3 are} SpSil can be carried out in accordance with the following stages I to III: stage I

wherein Sil and X are as defined above; Sp '' has the same meaning as defined for Sp above, except that it has a degree of unsaturation that is one higher than that of Sp. In other words, if Sp '' has a double bond, Sp is saturated and if Sp "has a triple bond or two double bonds, Sp has a double bond. Level II

wherein Sil, Sp and X are as defined above. Stage III

wherein Sil, Sp and X are as defined above.

The first stage is a hydrosilylation reaction and can be carried out using methods known per se, e.g. B. at a temperature in the range of 0 to 200 ° C, preferably 40 to 110 ° C in the presence of a metal catalyst. The reaction is preferably carried out in an inert gas atmosphere, if appropriate in a solvent. Suitable catalysts are platinum catalysts, such as metallic Pt on carbon, chloroplatinic acid, divinyltetramethyldisiloxane platinum complex or any other platinum complex; Rhodium catalysts such as 5% metallic Rh on carbon, bis (1,5-cyclooctadiene) di-Rh (I) dichloride and the like; Mo, Ru, Pd, Cr, Fe, Co, Ni or Cu in their metallic form or as a complex. The catalysts can be homogeneous or heterogeneous. Most organic solvents can be used, such as aromatic solvents, preferably toluene, xylene, pyridine; Ethers such as THF, dioxane and the like; aliphatic solvents such as dichloroethane, dichloromethane, chloroform, CCl ₄ , acetonitrile, DMF, DMSO, ethanol and the like.

The second stage is a transesterification or amide formation and can be carried out according to methods known per se using a catalyst II. Thus the reaction can be carried out at a temperature in the range from 50 to 250 ° C., optionally in a solvent. Organic solvents as listed in the first step can be used. Suitable catalysts are basic catalysts such as KOH, Na ₂ CO ₃ and the like, acidic catalysts such as H ₂ SO ₄ , HCl and the like or a Lewis acid catalyst such as e.g. B. Tetraisopropyl orthotitanate.

The third stage can be achieved by slowly treating the product of the second stage and cyanuric acid chloride at a temperature in the range from 20 to 280 ° C., preferably 50 to 150 ° C., with or without a suitable solvent (e.g. toluene, xylene) , A base may optionally be present, such as K ₂ CO ₃ , NaH and the like.

The order of the stages can be freely exchanged, e.g. B. it is possible to start with stage III by treating cyanuric acid chloride with 4-aminobenzoic acid-C ₁ -C ₆ alkyl ester, which is followed by a transesterification or amide formation (stage II), and to end with the hydrosilylation stage I.

worin X, Sp und Sil wie oben definiert sind, bei einer Temperatur im Bereich von 20 bis 280°C, oder Cyanursäurechlorid wird zuerst mit einer Verbindung der Formel A bei einer Temperatur im Bereich von 0 bis 40°C und dann mit 4-Aminobenzoesäure-C₁-C₂₀-alkylester bei einer Temperatur im Bereich von 20 bis 280°C behandelt.The synthesis of the compounds of the formula I in which one or two of the groups W ¹ , W ² and W ^{3 are} C ₁ -C ₂₀ -alkyl and the remaining groups of W ¹ , W ² and W ^{3 are} SpSil can also be compared to the reaction scheme above. Cyanuric acid chloride is either treated first with C ₁ -C ₂₀ -alkyl 4-aminobenzoate at a temperature in the range from 0 to 40 ° C. and then with a compound of the formula A.

wherein X, Sp and Sil are as defined above, at a temperature in the range of 20 to 280 ° C, or cyanuric acid chloride is first with a compound of formula A at a temperature in the range of 0 to 40 ° C and then with 4-aminobenzoic acid -C ₁ -C ₂₀ alkyl ester treated at a temperature in the range of 20 to 280 ° C.

worin X und Sp wie oben definiert sind, Sil'' ein Polysiloxan wie oben definiert ist und R¹² eine divalente C₁-C₁₀-Alkylkette oder eine divalente C₃-C₁₀-Alkylkette ist, die gegebenenfalls durch mindestens ein Sauerstoffatom unterbrochen ist.Compounds of the formula I in which Sil is a polysiloxane are preferably prepared according to the following scheme:

wherein X and Sp are as defined above, Sil '' is a polysiloxane as defined above and R ^{12 is} a divalent C ₁ -C ₁₀ alkyl chain or a divalent C ₃ -C ₁₀ alkyl chain which is optionally interrupted by at least one oxygen atom ,

Compounds according to the invention are colorless or slightly yellowish liquids, Semi-liquids or crystalline compounds. They are particularly qualified as light protection agents because of their high absorption of UV-B light, their good solubility in organic solvents, especially in solvents that are commonly used used in the cosmetics industry, and because of the light weight and cheap access. You can combined with one or more known UV-Bund / or UV-A filters become.

The production of new light stabilizers, especially of preparations for skin protection and sunscreen preparations for daily cosmetics includes that incorporated a compound of formula I into a cosmetic base material will who for Light stabilizers are common is. If appropriate, can other UV-A or UV-B filters during this induction can be combined. Such a combination of UV filters can have a synergistic effect. The production such light stabilizers are well known to those skilled in the art known. The amount of compounds of general formula I and other known W filter is not critical, suitable amounts are about 0.5 to about 12%.

Suitable UV-B filters, i. H. substances with absorption maxima between about 290 and 320 nm are e.g. B. the following organic compounds belonging to the broadest classes of substances include:

• P-aminobenzoic acid derivatives, such as ethyl, propyl, butyl, isobutyl, octyldimethyl, amyldimethyl, ethoxylated ethyl, propoxylated ethyl glyceryl or ethyl glycosyl p-aminobenzoate and the like;
• - acrylates, such as 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate (octocrylene), ethyl 2-cyano-3,3-diphenyl acrylate and the like;
• - aniline derivatives, such as methylanilinium methosulfate and the like;
• - anthranilinic acid derivatives, such as menthyl anthranilate and the like;
• - benzophenone derivatives, such as benzophenone-1 to benzophenone-12 and the like.
• Camphor derivatives, such as methylbenzylidene camphor, 3-benzylidene camphor, camphorbenzalkonium methosulfate, polyacrylamidomethylbenzylidene camphor, sulfobenzylidene camphor, sulfomethylbenzylidene camphor, Te rephthalidendicamphersulfonic acid and the like;
• - cinnamate derivatives, such as octyl methoxycinnamate or ethoxyethyl methoxycinnamate, diethanolamine methoxycinnamate, Isoamyl methoxycinnamate and the like. Just like cinnamic acid derivatives, which are on siloxanes are bound;
• - bile acid, like Digalloyl trioleate and the like;
• - imidazole derivatives, such as phenylbenimidazole sulfonic acid and the like;
• - salicylate derivatives, such as isopropylbenzyl, benzyl, butyl, octyl, isooctyl or homomenthyl salicylate and the like;
• - triazole derivatives, such as drometriazole, hydroxydibutylphenyl, hydroxydiamylphenyl, hydroxyoctylphenyl or hydroxyphenylbenztriazole and the like;
• - triazone derivatives, such as octyltriazone and the like, and
• - Pigments, such as microparticulate TiO ₂ , ZnO and the like.

The formulation can continue to use UV-A filters included how

• - dibenzoylmethane derivatives, such as 4-tert-butyl-4'-methoxydibenzoylmethane and the like;
• - Triazine compounds, as in the European patent applications EP 0 693 483 A1 . EP 0 704 437 A2 . EP 0 704 444 A1 and EP 0 780 382 A1 described;
• Organosiloxane compounds, as in the European patent applications EP 0 538 431 B1 . EP 0 709 080 A1 and EP 0 358 584 B1 described;
• - Malonate, like in the European Patent application 98 114 262.3 described.

Particularly useful for effective UV absorption are combinations with Metallooxynanopigmenten, such as. B. titanium oxide, zinc oxide, Ceria, zirconia, iron oxide and mixtures thereof, the diameter of which is <100 nm.

The following Examples 1 to 15 explain the invention continues without its scope in any way to restrict.

Examples 8 and 9 are comparative examples. Example 16 relates to a sunscreen composition.

Example 1 Preparation of 2,4,6-trianilino-p- {carbo-4 '- (1,1,3,3,3-pentamethyldisiloxanyl) -1'-butyloxy} -1,3,5-triazine

a) First stage: production of 4- (1,1,3,3,3-pentamethyldisiloxanyl) -1-butanol

A 50 ml reaction flask was charged with 10.3 ml of 3-buten-l-ol and a catalytic amount of divinyltetramethyldisiloxane platinum complex under an inert atmosphere and heated to 60 ° C. 19.5 ml of pentamethyldisiloxane was slowly added via a dropping funnel. The reaction mixture was stirred at 75 to 80 ° C for 3 hours and then distilled at 110 to 115 ° C / 38 × 10 ² Pa over a 10 cm column. Yield 18.9 g (86% of theory) of a clear liquid.

b) Second stage: manufacturing of 4-aminobenzoic acid 4- (1,1,3,3,3-pentamethyldisiloxanyl) butyl ester

A 50 ml reaction flask was charged with 9.9 g of 4-aminobenzoic acid ethyl ester, 15.3 g of 4- (1,1,3,3,3-pentamethyldisiloxanyl) -1-butanol and 0.06 ml of tetraisopropyl orthotitanate and at 110 ° C / 90 × 10 ² Pa heated for 7 hours. The ethanol formed was then distilled off. The product was fractionated at 205 ° C / 0.06 x 10 ² Pa, giving 12.6 g (62% of theory) of a clear liquid.

c) Third stage: manufacturing of 2,4,6-trianilino-p-carbo-4 '- (1,1,3,3,3-pentamethyldisiloxanyl) -1'-butyloxy} -1,3,5- triazine

In a 400 ml reaction flask, 10.2 g of 4- (1,1,3,3,3-pentamethyldisiloxanyl) butyl 4-aminobenzoate were dissolved in 150 ml of toluene and dissolved at 0.degree. A solution of 1.83 g of cyanuric acid chloride in 60 ml of toluene was added slowly over 20 minutes. Then the reaction mixture was carefully heated to reflux temperature and stirred at this temperature for 48 hours. The solvent was then removed using a rotary evaporator and the residue was chromatographed over SiO ₂ in hexane / EtOAc = 9: 1. 3.5 g of a semi-crystalline product was isolated. UV 308 nm (133230), melting point 86-87 ° C.

d) Measurement of the solubility in Cétiol LC ^® (cocoyl caprylate caprate) and Crodamol DA ^® (diisopropyl adipate)

Supersaturated solutions of 2,4,6-trianilino-p- {carbo-4 '(1,1,3,3,3-pentamethyldisiloxanyl) -1'-butyloxy} -1,3,5-triazine in the above solvents were added prepared and treated in an ultrasonic bath for 5 minutes. After standing overnight at 25 ° C., the solution was filtered through a microfilter (Millipore, pore size 0.5 μm) and then a UV measurement was carried out in CH ₂ Cl ₂ . The extinctions were compared to the absorbance of the pure compound. The following solubilities were found: 11.2% in Cétiol LC ^® and> 26% in Crodamol DA ^® .

Examples 2 to 5 were included the process as described in Example 1.

Example 2 Preparation of 2,4,6-Trianilino-p- {carbo-4 '- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) -1'-butyloxy} -1,3,5- triazine

• a) First stage: Preparation of 4- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) -1-butanol using 1,1,1,3,5,5,5-heptamethyltrisiloxane. After distillation at 74-78 ° C / 0.1 × 10 ² Pa, 83% of a liquid product were obtained.
• b) Second stage: Preparation of 4-aminobenzoic acid 4- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) butyl ester by reaction of 4- (1,1,1,3,5,5,5 -Heptamethyltrisiloxanyl) -1-butanol with ethyl 4-aminobenzoate. After chromatography on SiO ₂ in hexane / EtOAc = 1.1 and evaporation of the starting material, a clear oil was obtained in a yield of 43%.
• c) Third stage: preparation of 2,4,6-trianilino-p- {carbo-4 '- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) -1'-butyloxy} -1,3 , 5-triazine by Reflux of 4-aminobenzoic acid 4- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) butyl ester and cyanuric acid chloride. After chromatography, 37% of the product was obtained. UV 308 nm (120459), melting point 115-118 ° C.
• d) Measurement of solubility in Cetiol LC ^® and Crodamol DA ^® : 19.1% in Cetiol LC ^® and 35.5% in Crodamol DA ^® .

Example 3 Preparation of 2,4,6-trianilino-p- {carbo-2'-methyl-3 '(1,1,3,3,3-pentamethyldisiloxanyl) -1'-propyloxy} -1,3,5- triazine

• a) First stage: Preparation of 3- (1,1,3,3,3-pentamethyldisiloxanyl) -2-methyl-l-propanol using 2-methallyl alcohol instead of 3-buten-l-ol. After distillation at 105 ° C / 40 × 10 ² Pa, 81% of a liquid product were obtained.
• b) Second stage: Preparation of 2-methyl-3- (1,1,3,3,3-pentamethyldisiloxanyl) propyl 4-aminobenzoate by reaction of 3- (1,1,3,3,3-pentamethyldisiloxanyl) -2-methyl-1propanol. A clear yellow oil was obtained in a yield of 27%.
• c) third stage: preparation of 2,4,6-trianilino-p- {carbo-2'-methyl-3 '- (1,1,3,3,3-pentamethyldisiloxanyl) -1'-propyloxy} -1, 3,5-triazine by heating at reflux of 4-aminobenzoic acid-2-methyl-3- (1,1,3,3,3-pentamethyldisiloxanyl) propyl ester and cyanuric acid chloride. After chromatography, 33% of the product was obtained. UV 308 nm (109184), melting point 118-120 ° C.
• d) Measurement of solubility in Cetiol LC ^® and Crodamol DA ^® : 16.8% in Cetiol LC ^® and> 34% in Crodamol DA ^® .

Example 4 Preparation of 2,4,6-trianilino-p- {carbo-5 '- (1,1,3,3,3-pentamethyldisiloxanyl) -1'-pentyloxy} -1,3,5-triazine

• a) First stage: Preparation of 5- (1,1,3,3,3-pentamethyldisiloxanyl) -1-pentanol using 4-penten-l-ol instead of 3-buten-l-ol. After distillation at 124-125 ° C / 39 × 10 ² Pa, 88% of a liquid product was obtained.
• b) Second stage: Preparation of 4- (1,1,3,3,3-pentamethyldisiloxanyl) pentyl 4-aminobenzoate by reaction of 5- (1,1,3,3,3-pentamethyldisiloxanyl) -1-pentanol instead of 4- (1,1,3,3,3-pentamethyldisiloxanyl) -1-butanol. On clear yellow oil was obtained in a yield of 63%.
• c) Third step: Preparation of 2,4,6-trianilino-p- {carbo-5 '- (1,1,3,3,3-pentamethyldisiloxanyl) -1'-pentyloxy} -1,3,5-triazine by heating of 4-aminobenzoic acid 5- (1,1,3,3,3-pentamethyldisiloxanyl) pentyl ester and cyanuric acid chloride at reflux. After chromatography, 20% of the product was obtained. UV 308 nm (137085), Melting point 119.5-21.5 ° C.
• d) Measurement of solubility in Cetiol LC ^® and Crodamol DA ^® : 6.2% in Cétiol LC ^® and 13% in Crodamol DA ^® .

Example 5 Preparation of 2,4,6-trianilino-p- {carbo-3 '- (1,1,3,3,3-pentamethyldisiloxanyl) -1'-propyloxy} -1,3,5-triazine

• a) First stage: Preparation of 3- (1,1,3,3,3-pentamethyldisiloxanyl) -1-propanol using allyl alcohol instead of 3-buten-l-ol. After distillation at 99-101 ° C / 41 × 10 ² Pa, 85% of a liquid product was obtained.
• b) Second stage: Preparation of 3-aminobenzoic acid 3- (1,1,3,3,3-pentamethyldisiloxanyl) propyl ester by reacting 3- (1,1,3,3,3-pentamethyldisiloxanyl) -1-propanol. A clear yellow oil was obtained in a yield of 14%.
• c) Third stage: Preparation of 2,4,6-trianilino-p- {carbo-3 '- (1,1,3,3,3-pentamethyldisiloxanyl) -1'-propyloxy} -1,3,5-triazine by heating 3- (1,1,3,3,3-pentamethyldisiloxanyl) propyl 3-aminobenzoate and refluxing cyanuric acid chloride. After chromatography, 32% of the product was obtained. UV 308 nm (111664), melting point 125-127 ° C.
• d) Measuring the solubility in Cétiol LC ^® and Crodamol DA®: 4.3% in Cétiol LC ^® and> 16% in Crodamol DA ^® .

Example 6 Preparation of 2,4,6-trianilino-p- {carbo-4 '- (triethylsilyl) -1'-but-3-enyloxy} -1,3,5-triazine

• a) First stage: Preparation of 4- (triethylsilyl) -1-but-3-enol A 50 ml reaction flask was dichloride with 1-buten-3-ol and a catalytic amount of bis- (1,5-cyclooctadiene) -di-Rh (I) and triphenylphosphine are charged under an inert atmosphere. triethylsilane was slowly over added a dropping funnel. The reaction mixture was at room temperature Stirred for 72 hours. 86% of a yellow liquid were received.
• b) Second stage: Preparation of 4-aminobenzoic acid (triethylsilyl) -1-but-3-enyl ester by reaction of 4-aminobenzoic acid ester and 4- (triethylsilyl) -1-but-3-enol. Yield: 69% of a clear liquid.
• c) Third stage: Preparation of 2,4,6-trianilino-p- {carbo-4 '- (triethylsilyl) -1'-but-3-enyloxy} -1,3,5-triazine

Example 7

Example 7 became analogous to example 6 manufactured.

Preparation of 2,4,6-trianilino-p- {carbo-4 '- (triethylsilyl) -1'-butyloxy} -1,3,5-triazine

• a) First stage: preparation of 4- (triethylsilyl) -1-butanol.
• b) Second stage: Preparation of 4-aminobenzoic acid (triethylsilyl) butyl ester.
• c) Third step: Preparation of 2,4,6-trianilino-p- {carbo-4 '- (triethylsilyl) -1'-butyloxy} -1,3,5-triazine.

Example 8 Preparation of 2,4,6-trianilino- (p-carboethoxy) -1,3,5-triazine as a reference compound without any silyl groups

A 750 ml reaction flask was added charged with 13.9 g of ethyl p-aminobenzoate, dissolved in 300 ml of p-cymene. A solution of 4.85 g of cyanuric acid chloride in 150 ml of p-cymene was slowly added over 20 minutes. A white one Suspension was formed. Then the reaction mixture became careful to reflux temperature (170 ° C) heated and stirred at this temperature for 20 hours. The Reaction mixture was at 0 ° C cooled, filtered and the residue washed with MTBE and recrystallized from toluene, which was 12.3 g (82%) white Crystals delivered. UV 308 nm (133,374), melting point 218-20 ° C, which is a low solubility announced.

Measurement of solubility in Cétiol LC ^® and Crodamol DA ^® : The solubilities were determined as described in Example 1 and it was found: 0.02% in Cétiol LC ^® and 0.2% in Crodamol DA ^® .

Example 9 Measurement of the Solubility of UVINUL T-150 in Cetiol LC ^® and Crodamol DA® for Comparison:

The solubilities were determined for the commercially available product Uvinul T-150 as a reference as described in Example 1. UVINUL T-150 was the most soluble compound in the known range. The following solubilities were found: 3.7 to 4.2% in Cétiol LC ^® and 10% in Crodamol DA ^® , which is lower than for the examples according to the invention. The melting point was 126-127.5 ° C.

Example 10 Preparation of 2,4,6-trianilino-p- {carbo-7 '- (triethylsilyl) -4'-oxaheptyloxy} -1,3,5-triazine

a) 4- (2-triethylsilanylethoxy) butanol:

A 50 ml reaction flask was charged with 11.6 ml (100 mmol) of 1,4-butanediol monovinyl ether and a catalytic amount of divinyltetramethyldisiloxane platinum complex under an inert atmosphere and heated to 60 ° C. 10.4 g (90 mmol) of triethylsilane were slowly added via a dropping funnel. The exothermic reaction mixture was stirred at 75 ° C for 18 hours and then distilled at 105 to 107 ° C / 20 m ^-1 kgs ^-2 over a 10 cm Vigreux column.

Yield 15.2 g (66% of theory) a clear liquid. Purity 98.7% according to gas chromatography.

b) 4- (2-triethylsilanylethoxy) butyl 4-aminobenzoate

The same reaction as in example 1b was carried out using the product of the above reaction instead of 4- (1,1,3,3,3-pentamethyldisiloxanyl) -1-butanol. A clear yellow oil was obtained in a yield of 65% after chromatography.

c) 2,4,6-Trianilino-p- {carbo-7 '- (triethylsilyl) -4'-oxaheptyloxy} -1,3,5-triazine

The reaction procedure of example 1c was repeated using the p-aminobenzoic acid ester obtained above instead of p-aminobenzoic acid 4- (pentamethyldisiloxanyl) butyl ester. After chromatography, 79% of product are obtained. UV 308 nm (ε = 117,723), Melting point 79-81 ° C.

d) measurement of solubility in cosmetic solvents:

The solubilities were determined as described in Example 1 and it was found: 31% in Cétiol LC ^® and 45% in Crodamol DR®:

Example 11 Preparation of 2,4,6-trianilino-p- {carbo-7 '- (1,1,3,3,3-pentamethyldisiloxanyl) -4'-oxaheptyloxy} -1,3,5-triazine

a) 7- (1,1,3,3,3-pentamethyldisiloxanyl) -4-oxaheptan-l-ol:

A 50 ml reaction flask was charged with 16 ml of 1,4-butanediol vinyl ether and a catalytic amount of divinyltetramethyldisiloxane platinum complex under an inert atmosphere and heated to 60 ° C. 22.8 ml of pentamethyldisiloxane was slowly added via a dropping funnel. The reaction mixture was stirred at 75 to 80 ° C for 18 hours and then distilled at 85 to 87 ° C / 20 m ^-1 kgs ^-2 over a 10 cm column. Yield 29 g (85% of theory) of a clear liquid.

b) 4-Nitrobenzoic acid 7- (1,1,3,3,3-pentamethyldisiloxanyl) -4-oxaheptyl ester

A 100 ml reaction flask was charged with 20 g of the above silylated alcohol in 34 ml of pyridine and stirred vigorously. 22.5 9 p-nitrobenzoic acid chloride was added slowly over 20 minutes. The reaction mixture was heated to 60 ° C and stirred for 1 hour. Then it was poured into ice water and extracted with CH ₂ Cl ₂ . The combined organic phases were washed with 1N HCl and saturated NaHCO ₃ solution, dried over Na ₂ SO ₄ and concentrated to give 20.2 g (65%) of a yellow liquid. MS: 370, 298, 150, 147, 120 (100%).

c) 4-Aminobenzoic acid 7- (1,1,3,3,3-pentamethyldisiloxanyl) -4-oxaheptyl ester

A 600 ml hydrogenation autoclave was charged with 20 g of the above ester in 280 ml of methanol and 0.7 g of acetic acid and 3 g of Raney Ni catalyst. This mixture was hydrogenated for 18 hours at room temperature and a pressure of 6.895 x 10 ⁵ m ^-1 kg s ^-2 . The mixture was filtered, partitioned between ethyl acetate and water and the organic phase concentrated to give 93% of a yellow liquid. MS: 383 (M ⁺ ), 340, 268, 208, 147, 120 (100%).

d) 2,4,6-Trianilino-p- {carbo-7 '- (1,1,3,3,3-pentamethyldisiloxanyl) -4'-oxaheptyloxy} -1,3,5-triazine

The reaction procedure of example 1c was repeated using the p-aminobenzoic acid ester obtained above instead of p-aminobenzoic acid 4- (pentamethyldisiloxanyl) butyl ester. After chromatography, 60% of the product are obtained. UV 308 nm (ε = 124'248), Melting point 74-76 ° C.

e) Measurement of solubility in cosmetic solvents:

The solubilities were determined as described in Example 1 and it was found: 28% in Cétiol LC ^® and 29.4% in Crodamol DA ^® .

Example 12 Preparation of 2,4-dianilino-p-carbo- (2'-ethylhexyloxy) -6-anilino-p- {carbo-7 '- (1,1,3,3,3-pentamethyldisiloxanyl) -4'oxaheptyloxy } -1,3,5-triazine

a) 2,4-Dianilino-p-carbo- (2'-ethylhexyloxy) -6-chloro-1,3,5-triazine

A 100 ml reaction flask was charged with 0.92 g of cyanuric acid chloride in 50 ml of THF. A solution of 1.2 g of 2-ethylhexyl p-aminobenzoate and 0.85 ml of diisopropylethylamine in 25 ml of THF was slowly added at 0 ° C. The mixture was slowly heated to 45 ° C. and again a solution of 1.2 g of 2-ethylhexyl p-aminobenzoate and 0.85 ml of diisopropylethylamine in 25 ml of THF was slowly added. After 18 hours the reaction mixture was partitioned between water and ethyl acetate. The organic phases were dried and concentrated to give 2.6 g of a crystalline product which was chromatographed on silica gel in hexane: ethyl acetate = 7: 3. 1.8 g (56%) of a white crystalline material was isolated. MS: 609 (M ⁺ ), 497, 385 (100%).

b) 2,4-dianilino-p-carbo- (2'-ethylhexyloxy) -6-anilino-p {carbo-7 '- (1,1,3,3,3-pentamethyldisiloxanyl) -4'-oxaheptyloxy} - 1,3,5-triazine

A 25 ml reaction flask was used 0.61 g of the above dianilinotriazine in 15 ml of toluene and loaded Heated to 65 ° C. A solution of 0.38 g of 4- aminobenzoic acid 7- (1,1,3,3,3-pentamethyldisiloxanyl) -4-oxaheptanyl ester (see Example 11c) in 3 ml of toluene was added and the mixture 7 hours at 75 ° C touched. Then the reaction mixture was concentrated and on silica gel in hexane : Ethyl acetate = 7: 3 chromatographed, giving 46% of a white crystalline Product delivered. UV 308 nm (ε = 112,526), melting point 107-109 ° C.

c) Measurement of solubility in cosmetic solvents:

The solubilities were determined as described in Example 1 and it was found: 22% in Cétiol LC ^® and> 36% in Crodamol DA ^® .

Example 13 Preparation of 2,4-dianilino-p-carbo- (2'-ethylhexyloxy) -6-anilino-p- {carbo-7 '- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) -4'-oxaheptyloxy} -1,3,5-triazine

a) 7- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) -4-oxaheptanol:

A 50 ml reaction flask was charged with 11.6 g of 1,4-butanediol vinyl ether and a catalytic amount of divnyltetramethyldisiloxane platinum complex under an inert atmosphere and heated to 80 ° C. 20 g of heptamethyltrisiloxane was slowly added via a dropping funnel. The reaction mixture was stirred at 85 ° C for 4 hours and then distilled at 110-112 ° C / 25 m ^-1 kgs ^-2 over a 10 cm column. Yield 22.1 g (73% of theory) of a clear liquid.

b) 4-nitrobenzoic acid 7- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) -4-oxaheptyl ester:

A 25 ml reaction flask was charged with 8 g of the above silylated alcohol in 10.5 ml of pyridine and stirred vigorously. 7 g of p-nitrobenzoic acid chloride was added slowly over 20 minutes. The reaction mixture was heated to 60 ° C and stirred for 1 hour. Then it was poured onto ice water and extracted three times with CH ₂ Cl ₂ . The combined organic phases were washed with 1N HCl and saturated NaHCO ₃ solution, dried over Na ₂ SO ₄ and concentrated to give 9.9 g (86%) of a yellow liquid.

c) 4-Aminobenzoic acid 7- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) -4-oxaheptyl ester

A 300 ml hydrogenation autoclave was charged with 9.7 g of the above ester in 115 ml of methanol and 0.3 g of acetic acid and 1.2 g of Raney Ni catalyst. This mixture was hydrogenated for 18 hours at room temperature and a pressure of 6.895 x 10 ⁵ m ^-1 kgs ^-2 . The mixture was then filtered, partitioned between ethyl acetate and water and the organic phase concentrated to give 8.3 g (91%) of a yellow liquid. MS: 457 (M ⁺ ), 342, 268, 221, 208, 137, 120 (100%).

d) 2,4-dianilino-p-carbo- (2'-ethylhexyloxy) -6-anilino-p {carbo-7 '- (1,1,1,3,5,5,5,5-heptamethyltrisiloxanyl) -4' -oxaheptyloxy} -1,3,5-triazine

A 25 ml reaction flask was used 0.85 g 2,4-dianilino-pcarbo- (2'-ethylhexyloxy) -6-chloro-1,3,5-triazine (Preparation as described in Example 12a), dissolved in 15 ml of toluene, charged and at 65 ° C heated. A solution 0.7 g of 4- (aminobenzoic acid) 7- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) -4-oxaheptanyl ester (see above) in 3 ml of toluene was added and the mixture was 7.5 hours long at 75 ° C touched. Then the reaction mixture was concentrated and poured into silica gel Hexane: ethyl acetate = 7: 3 chromatographed, which was 1.13 g (79%) of a white delivered crystalline product. UV 308 nm (ε = 105,587), melting point 103-105 ° C.

e) Measurement of solubility in cosmetic solvents:

The solubilities were determined as described in Example 1 and found: 27% in Cétiol LC® and> 47% in Crodamol DA ^®.

Example 14 Preparation of 2,4-dianilino-p-carbo- (2'-ethylhexyloxy) -6-amino- {N- (2 '- (1,1,1,3,5,5,5,5-heptamethyltrisiloxanyl) allyl ) -pbenzamidyl} -1,3,5-triazine

a) 4-nitrobenzoic acid propargylamide

A 500 ml reaction flask comes with 19.8 ml propargylamine and 62 ml triethylamine in 150 ml methyl tert-butyl ether (MTBE) loaded. 55.2 g of p-nitrobenzoic acid chloride are dissolved in 100 ml MTBE solved and slowly added within 20 minutes. The reaction mixture is stirred vigorously for 90 minutes and then heated to 60 ° C for a further 30 minutes. Then it is filtered and the backlog washed with water, filtered again and recrystallized in acetonitrile, which gives 40.7 g of yellow crystals.

b) 4-aminobenzoic acid propargamide

A 1-1 reaction flask was used 33.5 g of 4-nitrobenzoic acid propargamide, solved in 410 ml of methanol and 410 ml of concentrated aqueous hydrochloric acid. 81.8 g of tin powder were added and the mixture was added for 165 minutes to 40 ° C heated. Then the reaction mixture was poured into a solution of 410 g of NaOH was poured into 1640 ml of ice water and the methanol was distilled off and it was filtered hot, to remove inorganic material. The product crystallized from this solution. It was recrystallized from ethanol / water, which was 21.5 g (75%) of the desired Materials supplied, melting point 122-125 ° C.

c) 4- (4,6-Dichloro- (1,3,5) -triazin-2-ylamino) -N- (propargyl-pbenzamide

A 75 ml reaction flask was charged with a cooled solution of 1.85 g of cyanuric acid chloride and 0.88 g of NaHCO ₃ in 20 ml of acetone. A solution of 1.77 g of 4-aminobenzoic acid propargylamide in 6 ml of acetone was slowly added at 0 ° C. The yellowish suspension was stirred for 30 minutes. Then 9 ml of water was added and the product filtered off, yielding 2.5 g of a yellowish powder. MS: 322 (M ⁺ ), 321, 292, 267 (100%).

d) 2,4-Dianilino-p-carbo- (2'-ethylhexyloxy) -6-amino- {N (propargyl) -p-benzamidyl} -1,3,5-triazine

A 25 ml reaction flask was charged with 1.04 g of 2-ethylhexyl paminobenzoate and 0.64 g of 4- (4,6-dichloro- (1,3,5) -triazin-2-ylamino) -N- (propargyl ) -p-benzamide obtained above, dispersed in 12 ml of xylene, charged and heated at reflux for 6 hours. The reaction mixture was cooled to 0 ° C. and the product was filtered off and recrystallized once from toluene. 0.98 g of a light yellow powder was obtained. UV 306 nm (111,436), MS: 747 (100%, M ⁺ ).

e) 2,4-Dianilino-p-carbo- (2'-ethylhexyloxy) -6-amino- {N- (2 '(1,1,1,3,5,5,5-heptamethyltrisiloxanyl) allyl) -p -benzamidyl} -1,3,5-triazine

A 25 ml reaction flask was used 1.23 g of the triazine obtained above in 19 ml of toluene, 0.45 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and a catalytic amount of divinyltetramethyldisiloxane platinum complex inert atmosphere fed. The reaction mixture was heated to 95 ° C. for 5 days, washed with water, concentrated and in hexane / ethyl acetate = 7: 3 Chromatograph. 0.25 g of gray-white crystals were isolated. UV 306 nm (e = 106,517), melting point 76-80 ° C.

f) measurement of solubility in cosmetic solvents:

The solubilities were determined as described in Example 1 and it was found:> 24% in Cétiol LC ^® and> 37% in Crodamol DA ^® .

Example 15 Preparation of a polysiloxane which corresponds in its statistical average to the following formula:

a) 4-nitrobenzoic acid-3-propanolamide

The reaction described in Example 14a was repeated using 2.5 equivalents of 3-aminopropanol instead of propargylamine and triethylamine. The reaction mixture was poured onto water and extracted seven times with ethyl acetate. The combined ethyl acetate phases were dried with Na ₂ SO ₄ and concentrated to give 73% of a crystalline product which was identified by NMR.

b) 4-nitrobenzoic acid-3-propargyloxypropylamide

A 100 ml reaction flask was added with 10 g of 4-nitrobenzoic acid-3-propargyloxypropylamide, solved in 70 ml of THF and 5.25 g of potassium tert-butoxide and 5.1 ml of propargyl bromide added. After 50 minutes the reaction mixture 5 hours at 60 ° C heated and then partitioned between water and ethyl acetate. The United organic phases were concentrated and in hexane / ethyl acetate = 9 : 1 chromatographed, giving 2.1 g of a yellow crystalline material provided, which in turn was identified by NMR.

c) 4-aminobenzoic acid-3-propargyloxypropylamide

The reaction described in Example 14b was repeated using 4-nitrobenzoic acid-3-propargyloxypropylamide instead of 4-nitrobenzoic acid-3-propargyloxypropylamide and heated to 35 ° C for only 15 minutes. The liquid portion of the reaction mixture was poured into water and extracted with CH ₂ Cl ₂ until no more product could be detected in the water phase. After concentration, a yellow honey is obtained in a yield of 97%, the structure of which was confirmed by N-MR. MS: 232 (M +), 193, 120 (100%).

d) 4- (4,6-dichloro- (1,3,5) triazin-2-ylamino) -N- (3-propargyloxypropyl-p-benzamide

The one described in Example 14c The reaction was repeated using 4-aminobenzoic acid-3-propargyloxypropylamide instead of 4-aminobenzoic acid propargamide. The product was filtered off, giving an off-white powder in 65.5% yield provided. MS: 379 (M +), 342, 340, 269, 267 (100%).

e) 2,4-Dianilino-p-carbo- (2'-ethylhexyloxy) -6-amino- {N- (3-propargyloxypropyl) -p-benzamidyl} -1,3,5-triazine

The one described in Example 14d The reaction was repeated using 4- (4,6-dichloro- (1,3,5) triazin-2-ylamino) -N- (3-propargyloxypropyl-p-benzamide, as described above, as a starting material. The raw product was chromatographed in hexane / ethyl acetate = 1: 1. A yellowish powder was obtained in a yield of 85%. UV 306 nm (ε = 104,380), Melting point 78-81 ° C.

f) Grafted with polysiloxane triazine

A 25 ml reaction flask was charged with 0.4 g of the triazine obtained above in 10 ml of toluene, 0.55 g of polysiloxane Ae-151 from Wacker-Chemie GmbH, and a catalytic amount of divinyltetramethyldisiloxane-platinum complex under an inert atmosphere. The reaction mixture was heated at 100 ° C. for 4 days, washed with water / methanol = 1:10, concentrated and chromatographed in hexane / ethyl acetate = 7: 3. 0.9 g of a yellowish liquid was isolated, which is freely miscible with Cétiol LC ^® or Crodamol DA ^® . UV 306 nm (E = 524).

Example 16

Production of an O / W sun protection lotion UV-B and UV-A

A sunscreen lotion with a wide Spectrum containing 2% of a compound from Example 1.

recipe:

Part A was opened in a reactor Heated to 85 ° C. Part B was added slowly over 10 minutes and then KOH admitted, cooled and degassed the emulsion.

Claims (17)

Compounds of the general formula I

wherein W ¹ , W ² and W ³ each independently represent C ₁ -C ₂₀ alkyl or a group SpSil; X ¹ , X ² and X ³ each independently represent 0 or NH; Sp represents a spacer group; Sil represents a silane, an oligosiloxane or a polysiloxane unit; with the proviso that at least one of the residues W ¹ , W ² and W ³ means SpSil. Compounds according to claim 1

wherein X represents O or NH; Sp 'is a straight-chain or branched saturated or mono- or polyunsaturated hydrocarbon group having 3 to 12 carbon atoms, Sil' means the group SiR ¹ R ² R ³ , in which R ¹ , R ² and R ^{3 are} each independently C ₁ -C ₆ -alkyl, C ₁ -C ₆ alkoxy or phenyl, or an oligosiloxane of the formula - SiMe _m (OSiMe ₃ ) _n , in which Me is methyl and m is 0, 1 or 2, n is 1, 2 or 3 and m + n 3 , or an oligosiloxane according to one of the formulas A, A 'and B

wherein Me is methyl and u is 0 to 6 means. Compounds according to Claim 1, in which W ¹ , W ² and W ^{3 are} SpSil or W ¹ and W ^{2 are} C ₁ -C ₂₀ -alkyl and W ^{3 is} SpSil. Compounds according to claim 1 or 3, wherein X ¹ , X ² and X ^{3 are} oxygen or X ¹ and X ^{2 are} oxygen and X ^{3 is} NH. Compounds according to any one of claims 1, 3 or 4, wherein the spacer is a divalent C ₃ -C ₁₂ alkyl or alkylene chain in which one or more carbon atoms have optionally been replaced by oxygen atoms. Compounds according to claim 5, wherein the spacer group - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH) (CH ₃ ) - (CH ₂ ) -, - (CH ₂ ) ₂ -CH = CH-, -C (= CH ₂ ) -CH ₂ -, -C (= CH ₂ ) - (CH ₂ ) ₂ -O- (CH ₂ ) ₄ -, (CH ₂ ) ₄ - O (CH ₂ ) ₂ - means. Compounds according to any one of claims 1 to 5, wherein the spacer group 3-propylene, 2-propylene, 2-propen-2-ylene, 2-propen-3-ylene, 2-methyl-3-propylene, 2-methyl-3-propenylene, 3-butylene, 4-butylene, 3-but-3-enylene, 4-but-3-enylene, 4-pentylene, 5-pentylene, 4-pent-4-enylene, 5-pent-4-enylene, 4- or 5- (3-methyl) penta-2,4-dienylene, 6-hexylene, 12-dodecylene or 11-dodecen-11-ylene. Compounds according to any one of claims 1 to 7, wherein the silane unit represents a group SiR ¹ R ² R ³ , wherein R ¹ , R ² and R ^{3 are} each independently C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or phenyl mean. Compounds according to claim 8, wherein the silane unit is -Si (CH ₂ -CH ₃ ) ₃ - or -Si (CH ₂ -CH ₂ -CH ₃ ) ₃ . Compounds according to any one of claims 1, 3 to 6, wherein the oligosiloxane is a group of the general formula. SiR ¹⁰ _m (OSiR ¹⁰ ₃ ) _n means with m = 0, 1 or 2; n = 3, 2 or 1 and m + n = 3 or a group of the general formula IIa, IIa 'or IIb

wherein A represents a bond to the spacer; R ^{10 represents} C ₁ -C ₆ alkyl or phenyl; r is 1 to 9, preferably 1 to 3. Compounds according to one of Claims 1, 3 to 6, in which the polysiloxane unit denotes a group of the general formulas IIIa or IIIb

wherein A is a bond to the spacer; R ^{11 represents} C ₁ -C ₆ alkyl or phenyl; s has a value of 4 to 250, preferably 5 to 150; t has a value of 5 to 250, preferably 5 to 150, more preferably a statistical mean of about 60; q has a value of 1 to 30, preferably 2 to 10, more preferably a statistical mean of about 4. Compounds according to claim 10 or 11, wherein R ¹⁰ and R ^{11 are} C ₁ -C ₆ alkyl, more preferably C ₁ -C ₄ alkyl, most preferably methyl. Compounds according to claim 1, namely 2,4,6-trianilino-p- {carbo-4 '- (1,1,3,3,3-pentamethyldisi-loxanyl) -1'-butyloxy} -1,3,5-triazine, 2,4,6-trianilino-p- {carbo-4 '- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) -1'-butyloxy} -1,3,5-triazine, 2,4,6-trianilino-p- {carbo-2'-methyl-3 '- (1,1,3,3,3-pentamethyldisiloxanyl) -1'-propyloxy} -1,3,5-triazine, 2,4,6-trianilino-p- {carbo-5 '- (1,1,3,3,3-pentamethyldisi-loxanyl) -1'-pentyloxy} -1,3,5-triazine, 2,4,6-trianilino-p- {carbo-3 '- (1,1,3,3,3-pentamethyldisi-loxanyl) -1'-propyloxy} -1,3,5-triazine, 2,4,6-trianilino-p- {carbo-4 '- (triethylsilyl) -1'-but-3-enyloxy} -1,3,5-triazine and 2,4,6-trianilino-p- {carbo-4 '- (triethylsilyl) -1'-butyloxy} -1,3,5-triazine. Compounds according to claim 1, namely 2,4,6-trianilino-p- {carbo-7 '- (triethylsilyl) -4'-oxaheptyloxy} -1,3,5-triazine, 2,4,6-trianilino-p- {carbo-7 '- (1,1,3,3,3-pentamethyldi-loxanyl) -4'-oxaheptyloxy} -1,3,5-triazine, 2,4-dianilino-p-carbo- (2'- ethylhexyloxy) -6-anilino-p {carbo-7 '- (1,1,3,3,3-pentamethyldisiloxanyl) -4'-oxaheptyloxy} -1, 3, 5-triazine, 2,4-dianilino-p-carbo- (2'-ethylhexyloxy) -6-anilino-p {carbo-7 '- (1,1,1,3,5,5,5-heptamethyltrisiloxanyl) -4'oxaheptyloxy} -1,3,5-triazine, 2,4-dianilino-p-carbo- (2'-ethylhexyloxy) -6-amino {N- (2 '(1,1,1,3,5,5,5- heptamethyltrisiloxanyl) allyl) -p-benzamidyl} -1,3,5-triazine or a polysiloxane which corresponds on a statistical average to the following formula:

Sunscreen composition containing one or more compounds according to one of claims 1 to 14 in an amount of 0.1 to 20 wt .-% based on the composition, which may also contain known UV-A or UV-B filters. A process for the preparation of the compounds of formula I according to claim 1, the process comprising: a) that a hydrosilane, oligohydrosiloxane or polyhydrosiloxane compound of the formula Sil-H, wherein Sil is as defined in claim 1, with a compound Sp''XH wherein X is O or NH and Sp '' has the same meaning as Sp, except that it has a degree of unsaturation that is one higher than that of Sp at a temperature in the range of 0 to 200 ° C, preferably 40 to 110 ° C is reacted in the presence of a metal catalyst, a compound of the formula SilSpXH being obtained, b) SilSpXH, the product of step a), with 4-aminobenzoic acid C ₁ -C ₆ alkyl ester at a temperature in the range from 50 to 250 ° C is reacted in the presence of a basic, acidic or Lewis acid catalyst, a compound of formula A

is obtained in which X is O or NH and Sp and Sil are as defined in claim 1, c-1) cyanuric acid chloride with a compound of formula A at a temperature of 20 to 280 ° C, preferably 50 to 150 ° C with or without suitable Solvent is treated to give a compound of formula I wherein W ¹ , W ² and W ^{3 represent} a group SpSil, or c-2) cyanuric chloride either first with 4-aminobenzoic acid-C ₁ -C ₂₀ alkyl ester at one temperature in the range from 0 to 40 ° C. and then treated with a compound of the formula A above at a temperature in the range from 20 to 280 ° C. or cyanuric acid chloride first with a compound of the formula A above at a temperature in the range from 0 to 40 ° C and then treated with C ₁ -C ₂₀ alkyl 4-aminobenzoate at a temperature in the range from 20 to 280 ° C, whereby a compound of formula I is obtained, wherein one or two of the groups W ¹ , W ² and W ^{3 is} C ₁ -C ₂₀ alkyl and the lead groups of W ¹ , W ² and W ³ mean SpSil. Use of compounds according to one of claims 1 to 14 for the production of a light protection composition in particular for the preparation of a cosmetic composition that is suitable is to protect human skin from sun exposure.